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NAMED REACTIONS IN PHOSPHORUS CHEMISTRY:

  1. Michaelis-Arbuzov Reaction:
    Reaction of trialkylphosphite with alkyl halide to give phosphonate.
    (RO)3P + R'X ==heat==> (RO)2P(O)R' + RX
  2. Michaelis-Becker Reaction:
    Reaction of dialkylphosphite+base with alkyl halide to give phosphonate.
    (RO)2P(O)H + R'X ==base==> (RO)2P(O)R' + base.HX
  3. Abramov Reaction:
    Reaction of trialkylphosphite with aldehyde to give alpha-alkoxyphosphonate.
    (RO)3P + R'CHO ==heat==> (RO)2P(O)CH(OR)R'
  4. Pudovik Reaction:
    Reaction of dialkylphosphite+base with aldehyde to give alpha-hydroxyphosphonate.
    (RO)2P(O)H + R'CHO ==base==> (RO)2P(O)CH(OH)R'
  5. Atherton-Todd Reaction:
    Reaction of dialkylphosphite+base with CCL4 to give chlorophosphate.
    (RO)2P(O)H + CCL4 ==base==> (RO)2P(O)CL + CHCL3
  6. Perkow Reaction:
    Reaction of trialkylphosphite with alpha-keto-alkyl halide to give vinyl-phosphate.
    (RO)3P + R'COCH2X ==heat==> (RO)2P(O)OC(=CH2)R' + RX
  7. Wittig Reaction:
    Reaction of phosphorus ylide with aldehyde to give alkene.
    R3P=CHR' + R"CHO ====> R3P=O + R'CH=CHR"

    [The following two variations were suggested by Parva Purohit from parva_99@yahoo.com on 11-Jan-2004]
    (a) When the ylide is replaced with a phosphine oxide carbanion, the reaction is referred to as the Horner reaction: L. Horner et al., Ber. 91, 61 (1958); Ber. 92, 2499 (1959).
    (b) When the ylide is replaced with a phosphonate carbanion, the reaction is referred to as the Horner-Emmons-Wadsworth reaction: W. S. Wadsworth, Jr., W. D. Emmons, J. Am. Chem. Soc. 83, 1733 (1961).
    Mitsunobu Reaction
    (suggested by Ciao/Kami from rose_petal2000_2000@yahoo.com on 10-Oct-2003)
    PPh3 + EtO2CN=NCO2Et is used as dehydration agents for R2NH + R'OH ==>R2 NR'
    Mitsunobu, O.; Yamada, M. Bull. Chem. Soc. Jpn., 1967, 40, 2380; Mitsunobu, O. Synthesis, 1981, 1.

    Pistschimuka Reaction
    (suggested by Terry Bidleman from terry.bidleman@ec.gc.ca on 24-Aug-2004)
    (RO)3P=S + RI ==heat==> (RO)2P(O)(SR) + RI
    Also called thiono-thiolo rearrangement.
    P. Pistschimuka, Ber. 41: 3854 (1908) and J. Pr. Chem. 84: 746 (1911).
    Referred in the following:
    C. Fest and K.-J. Schmidt, The Chemistry of Organophosphorus Pesticides, Reactivity, Synthesis, Mode of Action and Toxicology (Springer-Verlag, 1973), pages 36-37.
    M. Eto, M. Sasaki, M. Iio, M. Eto, H. Ohkawa, Tetrahedron Lett., (45), 4263-6, (1971).
    A. Schmidpeter, H. Groeger, Chem. Ber., 100 (12), 3979-91 (1967).


If any named phosphorus reaction is missing, please email me!


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Created by Dr. A. CHANDRASEKARAN. (Last Modified on 08-Sep-2004)
Department of Chemistry, University of Massachusetts, Amherst, MA 01003, USA.
Suggestions Welcome!